EP1773765A2 - Method for catalytic hydrogenation purification of lactam containing chorolactam impurities - Google Patents

Method for catalytic hydrogenation purification of lactam containing chorolactam impurities

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Publication number
EP1773765A2
EP1773765A2 EP05788450A EP05788450A EP1773765A2 EP 1773765 A2 EP1773765 A2 EP 1773765A2 EP 05788450 A EP05788450 A EP 05788450A EP 05788450 A EP05788450 A EP 05788450A EP 1773765 A2 EP1773765 A2 EP 1773765A2
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EP
European Patent Office
Prior art keywords
lactam
amine
solvent
impurities
catalyst
Prior art date
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EP05788450A
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German (de)
French (fr)
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EP1773765B1 (en
Inventor
Serge Hub
Eric Lacroix
Philippe Bonnet
Michel Devic
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Arkema France SA
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Arkema France SA
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Publication of EP1773765A2 publication Critical patent/EP1773765A2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
    • C07D201/16—Separation or purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
    • C07D201/14—Preparation of salts or adducts of lactams

Definitions

  • the present invention relates to a method for purifying cyclic lactams containing chlorolactam impurities by catalytic hydrogenation reaction.
  • Polyamides prepared from impure lactams thus show a tendency to yellowing and have a broad spectrum of molecular weights.
  • the nature of the impurities depends on the method of synthesis of the lactam used.
  • the lactam prepared by photo-oximation contains chlorine impurities specific for this type of process (chlorolactams), the presence of which degrades the properties of the polymers manufactured.
  • JP Sho 47-37633 / 72 proposes a catalyst based on Ni and BaF 2 deposited on SiO 2 .
  • the life of this catalyst is better than that of the catalyst referred to, but nevertheless has a measurable deactivation.
  • Hydrogenation purification processes require hydrogen-inert solvents which, inter alia, preclude the use of aromatic compounds, which are generally much better lactam solvents.
  • JP Sho patent 46-23743 / 71 describes a hydrogenation process with aromatic solvents. To avoid the hydrogenation of the solvent, it recommends adding a soluble amine in the aromatic solvent medium. The amine serves just to inhibit the hydrogenation of the solvent and can therefore be used in small amounts compared to the chlorinated impurities present.
  • an alkaline hydroxide is added to the medium in at least stoichiometric amount relative to the initial organic chlorine to neutralize the acidity produced by the reaction.
  • the aim of the invention is to propose a new process for purifying cyclic lactams containing 6 to 12 carbon atoms and containing chlorolactams as impurities, by hydrogenation reaction in the presence of a metal catalyst, a solvent and a a compound having a residue -NH 2 , -NH- or -N ⁇ wherein
  • the residue -NH 2 , -NH- or -N ⁇ is that of an amine for capturing the HCl generated during the hydrogenation reaction
  • the organic solvent is a solvent capable of solubilizing the amine hydrochloride formed by the capture of HCl by the amine, and the molar ratio represented by the% of amine expressed in moles on the% of elemental organic chlorine in the form of chlorolactam expressed in mole, is greater than or equal to 0.5.
  • the molar ratio is between 1 and 100 and preferably between 5 and 40.
  • the amine is tert-octylamine.
  • the organic solvent is selected from the group consisting of acyclic or cyclic aliphatic saturated hydrocarbon solvents. preferably cyclohexane, aromatic solvents, ionic liquids.
  • the invention also relates to a process for purifying cyclic lactams containing 6 to 12 carbon atoms and containing chlorolactams as impurities, by hydrogenation reaction in the presence of a metal catalyst, a solvent and a compound having an -NH- residue in which the -NH- residue is that of the lactam present or formed during the hydrogenation reaction and the organic solvent is an ionic liquid capable of solubilizing the lactam hydrochloride formed.
  • an organic solvent is used in the purification process which is an ionic liquid chosen from the group consisting of ionic liquids comprising a dialkylimidazolium derivative of formula I or II
  • R is CH 3 , - (CH 2 ) n -CH 3 , -CH 2 -C n F 2n + I , phenyl with n being an integer of 1 to 10, and A is AlCl 3 , SbCl 3 F 2 , TaCl 5 , TaF 5 , NbCl 5 , TiCl 4 , B represents SbF 6 , BF 4 , PF 6 , CF 3 SO 3 .
  • the ionic liquid is formed by the combination of the dialkyl imidazolium cation of formula I with R as defined above and an hexafluoroborate anion BF 6 or an anion hexafluorophosphate PF 6 .
  • the process is carried out at a temperature of between 100 and 250 ° C.
  • the lactam to be purified is lauryl-lactam or caprolactam.
  • the lactam to be purified contains up to 5% by weight of chlorolactam.
  • the hydrogenation step is carried out by continuously passing a lactam flow into a solvent optionally containing the amine with hydrogen on a catalyst.
  • the process for purifying cyclic lactams containing 6 to 12 carbon atoms is carried out by removing the corresponding chlorolactams by hydrogenation reaction in the presence of a metal catalyst, an amine to capture the HCl formed during the reaction. hydrogenation in the form of amine hydrochloride and an organic solvent capable of solubilizing the amine hydrochloride formed.
  • This process improves the yields and the conversion rate of chlorolactam to lactam.
  • the lactam to be purified may contain up to 5% by weight of chlorolactam impurities relative to the weight of the committed lactam, preferably up to 1%, and more particularly up to 0.1% by weight.
  • the amine chosen is such that its salt with hydrochloric acid is totally or partially soluble in the reaction solvent used.
  • the solubility of the salt formed is particularly dependent on the amount of chlorolactam to be removed.
  • concentration of the lactam to be purified in the chosen solvent so as not to exceed the solubility of the amine salt formed.
  • the presence of such an amine makes it possible to avoid the deactivation of the catalyst.
  • the amine hydrochloride formed does not deposit on the catalyst because of its solubility in the solvent of the reaction used and therefore the catalyst does not deactivate or little.
  • the amount of amine used depends on the amount of elemental organic chlorine present in the medium as chlorolactam.
  • a molar ratio corresponding to the ratio between the amine% expressed in moles and the% of chlorolactam expressed in moles of elemental organic chlorine initially present in the solution is thus defined.
  • the molar ratio as defined above is greater than or equal to 0.5, preferably between 1 and 100, even between 5 and 40.
  • Any amine whose hydrochloride is soluble or partially soluble in an organic medium is used in the process, such as the linear or branched primary, secondary and tertiary alkylamines R 1 NH 2 , R 1 R 2 NH and R 2 R 2 R 3 N with
  • the amine is also totally or partially soluble in the organic solvent used.
  • tert-octylamine (CH 2 ) 3 C-CH 2 -C (CH 3 ) 2 NH 2 ] are preferred.
  • the organic solvent for solubilizing the amine hydrochloride is generally selected from the group consisting of acyclic or cyclic aliphatic saturated hydrocarbon solvents, aromatic solvents, ionic liquids.
  • the acyclic or cyclic aliphatic saturated hydrocarbon solvents are chosen from hexane, heptane, octane, nonane, decane, undecane, linear or branched dodecane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, optionally substituted cyclododecane and their mixtures, and preferably the chosen organic solvent. is cyclohexane.
  • the aromatic solvents are chosen from benzene, toluene, ethylbenzene, xylenes, cumene and their mixtures.
  • the ionic liquids used in the invention are described for example in the patent application No. WO 01/83353 (page 1 to page 4 and the examples). Ionic liquids comprising a dialkylimidazolium derivative of formula I or II will be preferred.
  • R is CH 3 , - (CH 2 ) n -CH 3 , -CH 2 -C n F 2n + I , phenyl with n being an integer of 1 to 10, and A is AlCl 3 , SbCl 3 F 2 , TaCl 5 , TaF 5 , NbCl 5 , TiCl 4 , B represents SbF 6 , BF 4 , PF 6 , CF 3 SO 3 .
  • the ionic liquids formed by the combination of the dialkyl imidazolium cation of formula I with R as defined above and an hexafluoroborate anion BF 6 or an anion hexafluorophosphate PF 6 will also be preferred.
  • the solvents of the group consisting of acyclic or cyclic aliphatic saturated hydrocarbon solvents, or the ionic liquids mentioned above, will be used.
  • Any supported or bulk metal based hydrogenation catalyst can be used in the process, but it is preferred to use a Ni or Pd catalyst deposited on alumina, silica, silica-alumina or coal.
  • the working temperature is in general less than the decomposition temperature of the amine salt, and preferably between 100 and 250 ° C.
  • the pressure may be between 1 and 100 bar, preferably between 5 and 50 bar, and more particularly between 10 and 40 bar.
  • the purification process according to the invention can be used to purify the cyclic lactams containing chlorolactams as impurities, in particular lactams C 6 (caprolactam), or C 12 (lauryl-lactam), basic monomers in the synthesis of polyamides.
  • the invention provides a process for purifying cyclic lactams containing 6 to 12 carbon atoms having chlorolactams as impurities, by hydrogenation reaction in the presence of a metal catalyst, a solvent and a a compound having an -NH- residue in which the -NH- residue is that of the lactam present or formed during the hydrogenation reaction and the organic solvent is selected from ionic liquids as defined above.
  • the ionic liquid is capable of solubilizing the lactam hydrochloride formed.
  • the presence of the ionic liquid makes it possible to avoid the deactivation of the catalyst and to improve the conversion efficiencies of chlorolactams to lactams.
  • the metal catalyst used here is Pd / C or Ni / SiO 2 .
  • the preferred ionic liquid is bmimPF s wherein the lactam hydrochloride formed during the reaction Hydrogenation between HCl and lactam is soluble at a rate of 3% at 25 ° C and 35% at 100 ° C.
  • the solubilized lactam hydrochloride does not deposit on the catalyst. The lifetime of the catalyst, conversion efficiencies of chlorolactam to lactam are thus improved.
  • the process for purifying lactams is a continuous process in which a flow rate of the lactam to be purified continuously in the solvent optionally containing the amine with hydrogen over a catalyst is passed through.
  • the hourly volume velocity can be between 0.1 and 10 hr "1 , but it is preferentially carried out between 1 and 5 hr " 1 .
  • a solution of cyclohexane containing 10% by weight of lauryllactam (MW 197) containing 0.085% by weight of chlorine in the form of chlorolauryllactam (ie 0.024% by mole of elemental organic chlorine) is prepared. This solution is then fed continuously (86 g / h) into the reactor with hydrogen (0.5 l / h) under a pressure of 20 bar and a temperature T of 150 0 C in a reactor containing a quantity Qc 40 ml of commercial hydrogenation catalyst Ni-NiO-
  • the mixture from the reactor is first decanted to separate the liquid and gaseous phases. Lauryllactam is then recovered after evaporation of the solvent. The crystals obtained are washed with water to remove the salts produced.
  • the amount of elemental organic chlorine initially present in the lactam in the form of chlorolauryllactam is measured, the amount of residual elemental organic chlorine remaining fixed on the lactam and the amount of chlorides recovered in the washings, all expressed in% by weight of elemental chlorine.
  • the chlorine balance is determined by the ratio
  • a possible defect of this chlorine balance (deviation from 100%) is synonymous with accumulation of product on the catalyst and thus a decrease in the life of the catalyst.
  • the molar ratio corresponding to the ratio of the% amine expressed in moles of tert-octylamine is determined.
  • Example Ic Under the reaction conditions described in Example Ic, a solution of cyclohexane containing 0.2% by weight of tert-octylamine (0.155 mol%) and 10% by weight of lauryllactam is fed.
  • the initial amount of organic chlorine in the lactam is 0.09% by weight (ie 0.025% by mole of elemental chlorine in the solution) and the residual content after purification is 0.026% by weight.
  • the amount of chlorides assayed in the washings is 0.01% by weight.
  • the chlorolactam conversion is then 53% and the chlorine balance is 80%.
  • a solution of cyclohexane containing 10% of lauryl lactam containing 0.0565% by weight of chlorine is prepared. This solution is then fed continuously (82 g / h) into the reactor with hydrogen (0.5 l / h) at 20 bar and 180 0 C in a reactor containing 40 ml of commercial hydrogenation catalyst 0, 5% Pd / C.
  • the mixture from the reactor is first decanted to separate the liquid and gaseous phases. Lauryllactam is then recovered after evaporation of the solvent. The crystals obtained are washed with water to remove the salts produced.
  • the amount of residual organic chlorine in the lactam (obtained by gas chromatography GC) is then 0.0337% by weight.
  • the amount of chlorides assayed in the washings is 0.01% by weight.
  • the chlorolactam conversion is then 85% and the chlorine balance is 100%.
  • Comparative Example 4c A solution of cyclohexane containing 10% by weight of lauryl lactam containing 0.103% by weight of chlorine is prepared. This solution is then fed continuously (82 g / h) into the reactor with hydrogen (0.5 l / h) at 20 bar and 180 0 C in a reactor containing 80 ml of commercial hydrogenation catalyst Ni NiO-SiO 2 -Al 2 O 3 .
  • the mixture from the reactor is taken at different reaction times.
  • the mixture is first decanted to separate the liquid and gaseous phases. Lauryllactam is then recovered after evaporation of the solvent. The crystals obtained are washed with water to remove the salts produced.
  • the performance of the reaction is evaluated here as a function of the contact time of the reactants.
  • Example 5 with ionic liquid and without amine In a stainless steel autoclave is charged under an argon atmosphere to be protected from moisture:
  • the autoclave is pressurized with 20 bar of hydrogen and the reaction medium is heated at 100 ° C. for 6 hours with stirring and under 20 bar of hydrogen.
  • the total chlorine content of the lactam after treatment and washing with water is 0.13% instead of 0.17% before treatment a conversion rate of chlorolactam to lactam of 23.5%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Hydrogenated Pyridines (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyamides (AREA)
  • Pyrrole Compounds (AREA)

Abstract

The invention concerns a method for purifying cyclic lactams containing 6 to 12 carbon atoms and containing chlorolactams as impurities, by hydrogenation reaction in the presence of a metal catalyst, a solvent and a compound having a radical -NH<SUB>2</SUB>, -NH- or -N< radical is that of a HCl capturing amino generated during the hydrgantation reaction, and the organic solvent is a solvent capable of solublizing the aminated hydrochloride formed by the capture of HCl by the amino; and the mol ratio represented by the percentage of amine expressed in mol over the percentage of elementary organic chlorine in the form of chlorolactam expressed in mols, is at least 0.5.

Description

PROCEDE DE PURIFICATION PAR HYDROGENATION CATALYTIQUE DE LACTAME CONTENANT DES IMPURETES CHLOROLACTAMES. PROCESS FOR THE CATALYTIC HYDROGENATION PURIFICATION OF LACTAM CONTAINING CHLOROLACTAM IMPURITIES
Domaine de l'invention.Field of the invention
La présente invention se rapporte à un procédé de purification de lactames cycliques contenant des impuretés chlorolactames par réaction d'hydrogénation catalytique.The present invention relates to a method for purifying cyclic lactams containing chlorolactam impurities by catalytic hydrogenation reaction.
Art antérieur et problème technique. La préparation de polyamides de haute qualité nécessite de disposer de lactames très purs. Des impuretés en faibles quantités, à peine décelables par l'analyse, provoquent une diminution de la qualité des polyamides.Prior art and technical problem. The preparation of high quality polyamides requires the availability of very pure lactams. Impurities in small quantities, hardly detectable by the analysis, cause a decrease in the quality of the polyamides.
Des polyamides préparés à partir de lactames impurs montrent ainsi une tendance au jaunissement et présentent un large spectre de poids moléculaires.Polyamides prepared from impure lactams thus show a tendency to yellowing and have a broad spectrum of molecular weights.
De plus, la nature des impuretés dépend du procédé de synthèse du lactame utilisé. Ainsi, le lactame préparé par photo-oximation contient des impuretés chlorées spécifiques de ce type de procédé (chlorolactames) , dont la présence dégrade les propriétés des polymères fabriqués.In addition, the nature of the impurities depends on the method of synthesis of the lactam used. Thus, the lactam prepared by photo-oximation contains chlorine impurities specific for this type of process (chlorolactams), the presence of which degrades the properties of the polymers manufactured.
L'élimination de ces impuretés chlorées est donc indispensable. Une des techniques de purification bien connue de l'homme de l'art est de traiter le lactame avec de l'hydrogène sur des catalyseurs d'hydrogénation. Cette réaction élimine le chlore sous forme d'HCl et permet ainsi de transformer les chlorolactames en lactames.The elimination of these chlorinated impurities is therefore essential. One of the purification techniques well known to those skilled in the art is to treat the lactam with hydrogen on hydrogenation catalysts. This reaction removes chlorine in the form of HCl and thus makes it possible to convert chlorolactams into lactams.
Cependant, selon le brevet JP Sho 47-31622/12, les catalyseurs d'hydrogénation classiques comme le Nickel de Raney se désactivent assez rapidement. Selon les auteurs, l'origine de cette désactivation est directement liée à la faible solubilité de l'HCl co-produit dans les milieux réactionnels traditionnellement utilisés (lactame/ solvants organiques) , bloquant les sites actifs du catalyseur. l'However, according to JP Sho 47-31622 / 12, conventional hydrogenation catalysts such as Raney Nickel deactivate quite rapidly. According to the authors, the origin of this deactivation is directly related to the low solubility of the HCl co-produced in the reaction mediums traditionally used (lactam / organic solvents), blocking the active sites of the catalyst. the
L'utilisation d'un catalyseur à base de nickel *modifié par du manganèse, en plus de l'ajout d'un "hydroxyde alcalin (pour neutraliser HCl produit) permet d'améliorer la durée de vie du système catalytique, sans pour autant être totalement satisfaisante.The use of a nickel catalyst modified with manganese * in addition to the addition of a "alkali metal hydroxide (for neutralizing HCl produced) improves the life of the catalyst system without to be totally satisfactory.
Le brevet JP Sho 47-37633/72 propose un catalyseur à base de Ni et de BaF2 déposé sur SiO2. La durée de vie de ce catalyseur est meilleure que celle du catalyseur cité en référence, mais elle présente néanmoins une désactivation mesurable.JP Sho 47-37633 / 72 proposes a catalyst based on Ni and BaF 2 deposited on SiO 2 . The life of this catalyst is better than that of the catalyst referred to, but nevertheless has a measurable deactivation.
Les procédés de purification par hydrogénation nécessitent des solvants inertes vis-à-vis de l'hydrogène, ce qui empêche entre autres l'utilisation de composés aromatiques, qui sont en général de bien meilleurs solvants du lactame. Le brevet JP Sho 46-23743/71 décrit pourtant un procédé d'hydrogénation avec des solvants aromatiques. Pour éviter l'hydrogénation du solvant, il préconise d'ajouter une aminé soluble dans le milieu solvant aromatique. L'aminé sert juste à inhiber l'hydrogénation du solvant et peut donc être utilisée en faibles quantités par rapport aux impuretés chlorées présentes. De plus, un hydroxyde alcalin est ajouté au milieu en quantité au moins stœchiométrique par rapport au chlore organique initial afin de neutraliser l'acidité produite par la réaction.Hydrogenation purification processes require hydrogen-inert solvents which, inter alia, preclude the use of aromatic compounds, which are generally much better lactam solvents. JP Sho patent 46-23743 / 71 however describes a hydrogenation process with aromatic solvents. To avoid the hydrogenation of the solvent, it recommends adding a soluble amine in the aromatic solvent medium. The amine serves just to inhibit the hydrogenation of the solvent and can therefore be used in small amounts compared to the chlorinated impurities present. In addition, an alkaline hydroxide is added to the medium in at least stoichiometric amount relative to the initial organic chlorine to neutralize the acidity produced by the reaction.
Il apparaît donc que la purification de lactame par hydrogénation nécessite l'ajout d'une solution d'hydroxyde alcalin et éventuellement d'une aminé lorsque le solvant du lactame est un aromatique. Cependant, la présence de ces ajouts n'empêche pas la désactivation des catalyseurs utilisés.It therefore appears that the purification of lactam by hydrogenation requires the addition of an alkaline hydroxide solution and optionally an amine when the solvent of the lactam is an aromatic. However, the presence of these additions does not prevent the deactivation of the catalysts used.
Sans vouloir être lié par une théorie, on peut penser que la désactivation des catalyseurs s'effectuerait vraisemblablement par cristallisation des sels chlorés formés sur le catalyseur.Without wishing to be bound by a theory, one can think that the deactivation of the catalysts would take place presumably by crystallization of the chlorinated salts formed on the catalyst.
Il existe donc un besoin d'améliorer ces procédés de purification des lactames par hydrogénation des chlorolactames et en particulier d'empêcher la désactivation des catalyseurs d'hydrogénation utilisés. Résumé de l'inventionThere is therefore a need to improve these processes for purifying lactams by hydrogenation of chlorolactams and in particular to prevent the deactivation of the hydrogenation catalysts used. Summary of the invention
L'invention a pour but de proposer un nouveau procédé de purification de lactames cycliques contenant 6 à 12 atomes de carbone et contenant des chlorolactames comme impuretés, par réaction d'hydrogénation en présence d'un catalyseur métallique, d'un solvant et d'un composé ayant un reste -NH2,- NH- ou -N< dans lequel,The aim of the invention is to propose a new process for purifying cyclic lactams containing 6 to 12 carbon atoms and containing chlorolactams as impurities, by hydrogenation reaction in the presence of a metal catalyst, a solvent and a a compound having a residue -NH 2 , -NH- or -N <wherein
-le reste -NH2, -NH- ou -N< est celui d'une aminé de capture de l'HCl généré pendant la réaction d'hydrogénation, etthe residue -NH 2 , -NH- or -N <is that of an amine for capturing the HCl generated during the hydrogenation reaction, and
-le solvant organique est un solvant capable de solubiliser le chlorhydrate d'aminé formé par la capture de l'HCl par l'aminé, et -le ratio molaire représenté par le % d'aminé exprimé en mole sur le % de chlore organique élémentaire sous forme de chlorolactame exprimé en mole, est supérieur ou égale à 0,5.the organic solvent is a solvent capable of solubilizing the amine hydrochloride formed by the capture of HCl by the amine, and the molar ratio represented by the% of amine expressed in moles on the% of elemental organic chlorine in the form of chlorolactam expressed in mole, is greater than or equal to 0.5.
Selon un mode de réalisation, le ratio molaire est compris entre 1 et 100 et de préférence compris entre 5 et 40.According to one embodiment, the molar ratio is between 1 and 100 and preferably between 5 and 40.
Selon un mode de réalisation, l'aminé est choisie parmi le groupe des alkylamines primaires, secondaires et tertiaires linéaires ou ramifiées RiNH2, R1R2NH, R1R2R3N avec Ri=CnH2n+I n=2 àAccording to one embodiment, the amine is chosen from the group of primary, secondary and tertiary linear or branched alkylamines RiNH 2 , R 1 R 2 NH, R 1 R 2 R 3 N with R 1 = C n H 2n + I n = 2 to
12, à 3, de préférence l'aminé est la tert-octylamine.12 at 3, preferably the amine is tert-octylamine.
Selon un mode de réalisation, le solvant organique est choisi parmi le groupe constitué par les solvants hydrocarbonés saturés aliphatiques acycliques ou cycliques de préférence le cyclohexane, les solvants aromatiques, les liquides ioniques.According to one embodiment, the organic solvent is selected from the group consisting of acyclic or cyclic aliphatic saturated hydrocarbon solvents. preferably cyclohexane, aromatic solvents, ionic liquids.
L'invention se rapporte aussi à un procédé de purification de lactames cycliques contenant 6 à 12 atomes de carbone et contenant des chlorolactames comme impuretés, par réaction d'hydrogénation en présence d'un catalyseur métallique, d'un solvant et d'un composé ayant un reste -NH- dans lequel, le reste -NH- est celui du lactame présent ou formé pendant la réaction d'hydrogénation et le solvant organique est un liquide ionique capable de solubiliser le chlorhydrate de lactame formé.The invention also relates to a process for purifying cyclic lactams containing 6 to 12 carbon atoms and containing chlorolactams as impurities, by hydrogenation reaction in the presence of a metal catalyst, a solvent and a compound having an -NH- residue in which the -NH- residue is that of the lactam present or formed during the hydrogenation reaction and the organic solvent is an ionic liquid capable of solubilizing the lactam hydrochloride formed.
Selon un mode préféré de réalisation on utilise dans le procédé de purification un solvant organique qui est un liquide ionique choisi parmi le groupe constitué par les liquides ioniques comprenant un dérivé dialkylimidazolium de formule I ou IIAccording to a preferred embodiment, an organic solvent is used in the purification process which is an ionic liquid chosen from the group consisting of ionic liquids comprising a dialkylimidazolium derivative of formula I or II
I II dans lesquelles R est un groupe CH3, - (CH2)n-CH3, -CH2-CnF2n+I , phényl avec n étant un entier compris entre 1 et 10 , et A représente AlCl3, SbCl3F2, TaCl5, TaF5, NbCl5, TiCl4, B représente SbF6, BF4, PF6, CF3SO3.Wherein R is CH 3 , - (CH 2 ) n -CH 3 , -CH 2 -C n F 2n + I , phenyl with n being an integer of 1 to 10, and A is AlCl 3 , SbCl 3 F 2 , TaCl 5 , TaF 5 , NbCl 5 , TiCl 4 , B represents SbF 6 , BF 4 , PF 6 , CF 3 SO 3 .
Selon un mode de réalisation, le liquide ionique est formé par l'association entre le cation dialkyl imidazolium de formule I avec R tel que défini ci-dessus et un anion hexafluoroborate BF6 ou bien un anion hexafluorophosphate PF6.According to one embodiment, the ionic liquid is formed by the combination of the dialkyl imidazolium cation of formula I with R as defined above and an hexafluoroborate anion BF 6 or an anion hexafluorophosphate PF 6 .
Selon un mode de réalisation, le procédé est mis en œuvre à une température comprise entre 100 et 2500C. Selon un mode de réalisation, le lactame à purifier est le lauryl-lactame ou le caprolactame. Selon un mode de réalisation, le lactame à purifier contient jusqu'à 5% en poids de chlorolactame.According to one embodiment, the process is carried out at a temperature of between 100 and 250 ° C. According to one embodiment, the lactam to be purified is lauryl-lactam or caprolactam. According to one embodiment, the lactam to be purified contains up to 5% by weight of chlorolactam.
Selon un mode de réalisation, l'étape d'hydrogénation s'effectue en faisant passer en continu un débit de lactame dans un solvant contenant éventuellement l'aminé avec de l'hydrogène sur un catalyseur.According to one embodiment, the hydrogenation step is carried out by continuously passing a lactam flow into a solvent optionally containing the amine with hydrogen on a catalyst.
Expose détaillé de l'invention.Detailed exposition of the invention.
Le procédé de purification de lactames cycliques contenant 6 à 12 atomes de carbone est mis en œuvre en éliminant les chlorolactames correspondants par réaction d'hydrogénation en présence d'un catalyseur métallique, d'une aminé pour capturer l'HCl formé pendant la réaction d'hydrogénation sous forme de chlorhydrate d'aminé et d'un solvant organique capable de solubiliser le chlorhydrate d'aminé formé.The process for purifying cyclic lactams containing 6 to 12 carbon atoms is carried out by removing the corresponding chlorolactams by hydrogenation reaction in the presence of a metal catalyst, an amine to capture the HCl formed during the reaction. hydrogenation in the form of amine hydrochloride and an organic solvent capable of solubilizing the amine hydrochloride formed.
Ce procédé améliore les rendements et le taux de conversion du chlorolactame en lactame.This process improves the yields and the conversion rate of chlorolactam to lactam.
Le lactame à purifier peut contenir jusqu'à 5% en poids de d' impuretés chlorolactame par rapport au poids du lactame engagé , de préférence jusqu'à 1%, et plus particulièrement jusqu'à 0.1% en poids.The lactam to be purified may contain up to 5% by weight of chlorolactam impurities relative to the weight of the committed lactam, preferably up to 1%, and more particularly up to 0.1% by weight.
L'aminé choisie est telle que son sel avec l'acide chlorhydrique est totalement ou partiellement soluble dans le solvant de réaction utilisé. La solubilité du sel formé est notamment dépendante de la quantité de chlorolactame à éliminer. Ainsi, pour effectuer la purification, on pourra choisir de manière appropriée la concentration du lactame à purifier dans le solvant choisi, de manière à ne pas dépasser la solubilité du sel d'aminé formé. La présence d'une telle aminé permet d'éviter la désactivation du catalyseur.The amine chosen is such that its salt with hydrochloric acid is totally or partially soluble in the reaction solvent used. The solubility of the salt formed is particularly dependent on the amount of chlorolactam to be removed. Thus, to carry out the purification, it will be possible to appropriately choose the concentration of the lactam to be purified in the chosen solvent, so as not to exceed the solubility of the amine salt formed. The presence of such an amine makes it possible to avoid the deactivation of the catalyst.
En effet le chlorhydrate d'aminé formé ne se dépose pas sur le catalyseur du fait de sa solubilité dans le solvant de la réaction utilisé et de ce fait le catalyseur ne se désactive pas ou peu.In fact, the amine hydrochloride formed does not deposit on the catalyst because of its solubility in the solvent of the reaction used and therefore the catalyst does not deactivate or little.
La quantité d'aminé utilisée dépend de la quantité de chlore organique élémentaire présent dans le milieu sous forme de chlorolactame.The amount of amine used depends on the amount of elemental organic chlorine present in the medium as chlorolactam.
On définit ainsi un ratio molaire correspondant au rapport entre le % d' aminé exprimé en mole et le % de chlorolactame exprimé en mole de chlore organique élémentaire présent initialement dans la solution. Le ratio molaire tel que défini ci-dessus est supérieur ou égal à 0,5 de préférence compris entre 1 et 100 voire compris entre 5 et 40.A molar ratio corresponding to the ratio between the amine% expressed in moles and the% of chlorolactam expressed in moles of elemental organic chlorine initially present in the solution is thus defined. The molar ratio as defined above is greater than or equal to 0.5, preferably between 1 and 100, even between 5 and 40.
On utilise dans le procédé toute aminé, dont le chlorhydrate est soluble ou partiellement soluble en milieu organique, comme les alkylamines primaires, secondaires et tertiaires linéaires ou ramifiés RiNH2, R1R2NH, R2R2R3N avec Any amine whose hydrochloride is soluble or partially soluble in an organic medium is used in the process, such as the linear or branched primary, secondary and tertiary alkylamines R 1 NH 2 , R 1 R 2 NH and R 2 R 2 R 3 N with
Selon un mode particulier de réalisation, l'aminé est aussi soluble totalement ou partiellement dans le solvant organique utilisé.According to a particular embodiment, the amine is also totally or partially soluble in the organic solvent used.
On préfère les aminés primaires et en particulier la tert- octylamine [ (CH2)3C-CH2-C (CH3) 2NH2] .Primary amines and in particular tert-octylamine [(CH 2 ) 3 C-CH 2 -C (CH 3 ) 2 NH 2 ] are preferred.
Le solvant organique pour solubiliser le chlorhydrate d'aminé est en général choisi parmi le groupe constitué par les solvants hydrocarbonés saturés aliphatiques acycliques ou cycliques, les solvants aromatiques, les liquides ioniques.The organic solvent for solubilizing the amine hydrochloride is generally selected from the group consisting of acyclic or cyclic aliphatic saturated hydrocarbon solvents, aromatic solvents, ionic liquids.
Les solvants hydrocarbonés saturés aliphatiques acycliques ou cycliques sont choisis parmi hexane, heptane, octane, nonane, décane, undécane, dodécane linéaires ou ramifiés, cyclohexane, cycloheptane, cyclooctane, cyclodécane, cyclododécane éventuellement substitués et leurs mélanges, et de préférence le solvant organique choisi est le cyclohexane.The acyclic or cyclic aliphatic saturated hydrocarbon solvents are chosen from hexane, heptane, octane, nonane, decane, undecane, linear or branched dodecane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, optionally substituted cyclododecane and their mixtures, and preferably the chosen organic solvent. is cyclohexane.
Les solvants aromatiques sont choisis parmi benzène, toluène, ethylbenzène, xylènes, cumène et leurs mélanges. Les liquides ioniques utilisés dans l'invention sont décrits par exemple dans la demande de brevet n° WO 01/83353 (page 1 à page 4 et les exemples) . On préférera les liquides ioniques comprenant un dérivé dialkylimidazolium de formule I ou IIThe aromatic solvents are chosen from benzene, toluene, ethylbenzene, xylenes, cumene and their mixtures. The ionic liquids used in the invention are described for example in the patent application No. WO 01/83353 (page 1 to page 4 and the examples). Ionic liquids comprising a dialkylimidazolium derivative of formula I or II will be preferred.
I II dans lesquelles R est un groupe CH3, -(CH2)n-CH3, -CH2-CnF2n+I , phenyl avec n étant un entier compris entre 1 et 10 , et A représente AlCl3, SbCl3F2, TaCl5, TaF5, NbCl5, TiCl4, B représente SbF6, BF4, PF6, CF3SO3.Wherein R is CH 3 , - (CH 2 ) n -CH 3 , -CH 2 -C n F 2n + I , phenyl with n being an integer of 1 to 10, and A is AlCl 3 , SbCl 3 F 2 , TaCl 5 , TaF 5 , NbCl 5 , TiCl 4 , B represents SbF 6 , BF 4 , PF 6 , CF 3 SO 3 .
On préférera encore les liquides ioniques formés par l'association entre le cation dialkyl imidazolium de formule I avec R tel que défini ci-dessus et un anion hexafluoroborate BF6 ou bien un anion hexafluorophosphate PF6.The ionic liquids formed by the combination of the dialkyl imidazolium cation of formula I with R as defined above and an hexafluoroborate anion BF 6 or an anion hexafluorophosphate PF 6 will also be preferred.
Selon un mode de réalisation préféré, on utilisera les solvants du groupe constitué par les solvants hydrocarbonés saturés aliphatiques acycliques ou cycliques, ou bien les liquides ioniques cités ci-dessus.According to a preferred embodiment, the solvents of the group consisting of acyclic or cyclic aliphatic saturated hydrocarbon solvents, or the ionic liquids mentioned above, will be used.
Tout catalyseur d'hydrogénation à base de métaux déposés sur un support ou massique peut être utilisé dans le procédé, mais on préfère utiliser un catalyseur à base de Ni ou de Pd déposé sur alumine, silice, silice-alumine ou charbon.Any supported or bulk metal based hydrogenation catalyst can be used in the process, but it is preferred to use a Ni or Pd catalyst deposited on alumina, silica, silica-alumina or coal.
La température de travail est en général inférieure à la température de décomposition du sel d'aminé, et de préférence comprise entre 100 et 2500C.The working temperature is in general less than the decomposition temperature of the amine salt, and preferably between 100 and 250 ° C.
La pression peut être comprise entre 1 et 100 bar, de préférence entre 5 et 50 bar, et plus particulièrement entre 10 et 40 bar. l'The pressure may be between 1 and 100 bar, preferably between 5 and 50 bar, and more particularly between 10 and 40 bar. the
Le procédé de purification selon l'invention peut être mis en œuvre pour purifier les lactames cycliques contenant des chlorolactames comme impuretés, en particulier les lactames en C6 (caprolactame) , ou en C12 (lauryl-lactame) , monomères de base dans la synthèse des polyamides.The purification process according to the invention can be used to purify the cyclic lactams containing chlorolactams as impurities, in particular lactams C 6 (caprolactam), or C 12 (lauryl-lactam), basic monomers in the synthesis of polyamides.
En effet, l'utilisation d'un tel procédé pour la purification des lactames permet d'éliminer les chorolactames en les transformant en lactames et, du fait de la présence d'aminé, d'empêcher la capture de HCl généré lors de l'hydrogénation par le lactame lui-même. Par conséquent, ce procédé permet d'éviter le dépôt du chlorhydrate de lactame sur le catalyseur, dans les cas très fréquents où ce sel est insoluble dans le milieu réactionnel . Ainsi la présence de l'aminé permet d'éviter la désactivation du catalyseur et d'améliorer les rendements de conversion des chlorolactames en lactames.In fact, the use of such a process for the purification of lactams makes it possible to eliminate chorolactams by transforming them into lactams and, because of the presence of amine, to prevent the capture of HCl generated during the treatment. hydrogenation by the lactam itself. Consequently, this process makes it possible to avoid the deposition of lactam hydrochloride on the catalyst, in the very frequent cases where this salt is insoluble in the reaction medium. Thus, the presence of the amine makes it possible to avoid the deactivation of the catalyst and to improve the conversion efficiencies of chlorolactams to lactams.
Selon un autre mode de réalisation, l'invention propose un procédé de purification de lactames cycliques contenant 6 à 12 atomes de carbone ayant des chlorolactames comme impuretés, par réaction d'hydrogénation en présence d'un catalyseur métallique, d'un solvant et d'un composé ayant un reste -NH- dans lequel, le reste -NH- est celui du lactame présent ou formé pendant la réaction d'hydrogénation et le solvant organique est choisi parmi les liquides ioniques tels que définis précédemment. Le liquide ionique est capable de solubiliser le chlorhydrate de lactame formé.According to another embodiment, the invention provides a process for purifying cyclic lactams containing 6 to 12 carbon atoms having chlorolactams as impurities, by hydrogenation reaction in the presence of a metal catalyst, a solvent and a a compound having an -NH- residue in which the -NH- residue is that of the lactam present or formed during the hydrogenation reaction and the organic solvent is selected from ionic liquids as defined above. The ionic liquid is capable of solubilizing the lactam hydrochloride formed.
La présence du liquide ionique permet d'éviter la désactivation du catalyseur et d'améliorer les rendements de conversion des chlorolactames en lactames.The presence of the ionic liquid makes it possible to avoid the deactivation of the catalyst and to improve the conversion efficiencies of chlorolactams to lactams.
Selon un mode de réalisation préféré , le catalyseur métallique utilisé ici est le Pd/C ou le Ni/SiO2.According to a preferred embodiment, the metal catalyst used here is Pd / C or Ni / SiO 2 .
Le liquide ionique préféré est le bmimPFs dans lequel le chlorhydrate de lactame, qui se forme durant la réaction d'hydrogénation entre l'HCl et le lactame est soluble à raison de 3% à 25°C et 35% à 1000C. De ce fait, le chlorhydrate de lactame solubilisé ne se dépose pas sur le catalyseur. La durée de vie du catalyseur, les rendements de conversion du chlorolactame en lactame sont ainsi améliorés.The preferred ionic liquid is bmimPF s wherein the lactam hydrochloride formed during the reaction Hydrogenation between HCl and lactam is soluble at a rate of 3% at 25 ° C and 35% at 100 ° C. As a result, the solubilized lactam hydrochloride does not deposit on the catalyst. The lifetime of the catalyst, conversion efficiencies of chlorolactam to lactam are thus improved.
Selon un autre mode de réalisation, le procédé de purification des lactames est un procédé en continu dans lequel on fait passer un débit du lactame à purifier de manière continue dans le solvant contenant éventuellement l'aminé avec de l'hydrogène sur un catalyseur.According to another embodiment, the process for purifying lactams is a continuous process in which a flow rate of the lactam to be purified continuously in the solvent optionally containing the amine with hydrogen over a catalyst is passed through.
La vitesse volumique horaire peut être comprise entre 0,1 et 10 hr"1, mais on opère préfèrentiellement entre 1 et 5 hr"1.The hourly volume velocity can be between 0.1 and 10 hr "1 , but it is preferentially carried out between 1 and 5 hr " 1 .
Exemples.Examples.
Les exemples suivants illustrent la présente invention sans toutefois en limiter la portée. Les exemples dits comparatifs correspondent à des essais sans aminé.The following examples illustrate the present invention without, however, limiting its scope. The so-called comparative examples correspond to tests without amines.
Exemple comparatif Ic.Comparative Example Ic.
On prépare une solution de cyclohexane à 10% en poids de lauryllactame (PM 197) contenant 0,085% en poids de chlore sous forme de chlorolauryllactame (soit 0,024% en moles de chlore organique élémentaire) . Cette solution est ensuite alimentée en continu (86 g/h) dans le réacteur avec de l'hydrogène (0,5 1/h) sous une pression de 20 bar et une température T de 1500C dans un réacteur contenant une quantité Qc de 40 ml de catalyseur d'hydrogénation commercial Ni-NiO-A solution of cyclohexane containing 10% by weight of lauryllactam (MW 197) containing 0.085% by weight of chlorine in the form of chlorolauryllactam (ie 0.024% by mole of elemental organic chlorine) is prepared. This solution is then fed continuously (86 g / h) into the reactor with hydrogen (0.5 l / h) under a pressure of 20 bar and a temperature T of 150 0 C in a reactor containing a quantity Qc 40 ml of commercial hydrogenation catalyst Ni-NiO-
SiO2-Al2O3.SiO 2 -Al 2 O 3 .
Le mélange issu du réacteur est d'abord décanté pour séparer ies phases liquide et gazeuse. Le lauryllactame est ensuite récupéré après évaporation du solvant. Les cristaux obtenus sont lavés avec de l'eau pour éliminer les sels produits.The mixture from the reactor is first decanted to separate the liquid and gaseous phases. Lauryllactam is then recovered after evaporation of the solvent. The crystals obtained are washed with water to remove the salts produced.
Le chlore organique initialement fixé à un atome de carbone du lauryllactame se retrouve après le traitement à l'hydrogène sous forme HCl relié au lactame lui-même. Un lavage à l'eau permet de récupérer cet HCl qui peut alors être dosé sous forme de chlorures.The organic chlorine initially attached to a carbon atom of lauryllactam is found after treatment with hydrogen in HCl form linked to the lactam itself. A washing with water makes it possible to recover this HCl which can then be assayed in the form of chlorides.
On dose la quantité de chlore organique élémentaire initialement présent dans le lactame sous forme de chlorolauryllactame, la quantité de chlore organique élémentaire résiduel resté fixé sur le lactame et la quantité de chlorures récupérés dans les eaux de lavage, le tout exprimé en % en poids de chlore élémentaire.The amount of elemental organic chlorine initially present in the lactam in the form of chlorolauryllactam is measured, the amount of residual elemental organic chlorine remaining fixed on the lactam and the amount of chlorides recovered in the washings, all expressed in% by weight of elemental chlorine.
On détermine la conversion des chlorolactames par le rapport ;The conversion of chlorolactams by the ratio is determined;
% de chlore organique initial - % chlore organique résiduel% of initial organic chlorine -% residual organic chlorine
% de chlore organique initial.% of initial organic chlorine.
On détermine le bilan chlore par le rapportThe chlorine balance is determined by the ratio
% chlore organique résiduel + % des chlorures récupérés % chlore initial.% residual organic chlorine +% chlorides recovered% initial chlorine.
Un éventuel défaut de ce bilan chlore (écart par rapport à 100%) est synonyme d'accumulation de produit sur le catalyseur et donc de diminution de la durée de vie du catalyseur.A possible defect of this chlorine balance (deviation from 100%) is synonymous with accumulation of product on the catalyst and thus a decrease in the life of the catalyst.
On détermine le ratio molaire correspondant au rapport entre le % d'aminé exprimé en moles de tert octylamineThe molar ratio corresponding to the ratio of the% amine expressed in moles of tert-octylamine is determined.
(PM=129) et le % de chlorolauryllactame exprimé en moles de chlore organique élémentaire initialement présent dans la solution.(MW = 129) and% chlorolauryllactam expressed as moles of elemental organic chlorine initially present in the solution.
Le tableau suivant résume les résultats de conversion du chlorolactame en lactame ainsi que le bilan chlore en fonction des différents paramètres T, ratio molaire, % d'aminé en poids, quantité et type de catalyseur, durée de fonctionnement du réacteur en continu. The following table summarizes the results of conversion of chlorolactam to lactam and the chlorine balance according to the various parameters T, molar ratio,% amine by weight, amount and type of catalyst, reactor operating time continuously.
Exemple 1.Example 1
Dans les conditions de réaction décrites à l'exemple Ic, on alimente une solution de cyclohexane contenant 0,2% en poids de tert-octylamine (0,155% en moles) et 10% en poids de lauryllactame. La quantité initiale de chlore organique dans le lactame est de 0,09% en poids (soit 0,025% en moles de chlore élémentaire dans la solution) et la teneur résiduelle après purification est de 0,026% en poids. La quantité de chlorures dosée dans les eaux de lavage est 0,01% en poids.Under the reaction conditions described in Example Ic, a solution of cyclohexane containing 0.2% by weight of tert-octylamine (0.155 mol%) and 10% by weight of lauryllactam is fed. The initial amount of organic chlorine in the lactam is 0.09% by weight (ie 0.025% by mole of elemental chlorine in the solution) and the residual content after purification is 0.026% by weight. The amount of chlorides assayed in the washings is 0.01% by weight.
La conversion des chlorolactames est alors de 71% .The conversion of chlorolactams is then 71%.
Le bilan chlore est de 40%. Exemple 2.The chlorine balance is 40%. Example 2
Dans les conditions de réaction décrites ci-dessus, on alimente une solution de cyclohexane contenant 1% en poids de tert-octylamine (0,775% en mole) et 10% en poids de lauryllactame. La quantité initiale de chlore organique dans le lactame est de 0,077% en poids (soit 0,022% en moles dans la solution) et la teneur résiduelle après purification est de 0,036% en poids. La quantité de chlorures dosée dans les eaux de lavage est 0,025% en poids.Under the reaction conditions described above, a solution of cyclohexane containing 1% by weight of tert-octylamine (0.775% by mole) and 10% by weight of lauryllactam is fed. The initial amount of organic chlorine in the lactam is 0.077% by weight (ie 0.022 mol% in the solution) and the residual content after purification is 0.036% by weight. The amount of chlorides assayed in the washings is 0.025% by weight.
La conversion des chlorolactames est alors de 53% et le bilan chlore est de 80%.The chlorolactam conversion is then 53% and the chlorine balance is 80%.
Exemple comparatif 3c.Comparative Example 3c.
On prépare une solution de cyclohexane à 10% de lauryllactame contenant 0,0565% en poids de chlore. Cette solution est ensuite alimentée en continu (82 g/h) dans le réacteur avec de l'hydrogène (0,5 1/h) sous 20 bar et 1800C dans un réacteur contenant 40 ml de catalyseur d'hydrogénation commercial 0,5% Pd/C.A solution of cyclohexane containing 10% of lauryl lactam containing 0.0565% by weight of chlorine is prepared. This solution is then fed continuously (82 g / h) into the reactor with hydrogen (0.5 l / h) at 20 bar and 180 0 C in a reactor containing 40 ml of commercial hydrogenation catalyst 0, 5% Pd / C.
Le mélange issu du réacteur est d'abord décanté pour séparer les phases liquide et gazeuse. Le lauryllactame est ensuite récupéré après évaporation du solvant. Les cristaux obtenus sont lavés avec de l'eau pour éliminer les sels produits .The mixture from the reactor is first decanted to separate the liquid and gaseous phases. Lauryllactam is then recovered after evaporation of the solvent. The crystals obtained are washed with water to remove the salts produced.
La quantité de chlore organique résiduelle dans le lactame (obtenue par chromatographie en phase gazeuse CPG) est alors de 0,0337% en poids. La quantité de chlorures dosée dans les eaux de lavage est 0,01% en poids.The amount of residual organic chlorine in the lactam (obtained by gas chromatography GC) is then 0.0337% by weight. The amount of chlorides assayed in the washings is 0.01% by weight.
Exemple 3.Example 3
Dans les conditions de réaction décrites ci-dessus, on alimente une solution de cyclohexane contenant 1% en poids de tert-octylamine (0,775% en moles) et 10% de lauryllactame. La quantité initiale de chlore organique dans le lactame est de 0,073% en poids (soit 0,020% en moles dans la solution) et la teneur résiduelle après purification est de 0,011% en poids. La quantité de chlorure dosée dans les eaux de lavage est 0, 063% en poids .Under the reaction conditions described above, a solution of cyclohexane containing 1% by weight of tert-octylamine (0.775 mol%) and 10% lauryllactam. The initial quantity of organic chlorine in the lactam is 0.073% by weight (ie 0.020 mol% in the solution) and the residual content after purification is 0.011% by weight. The amount of chloride dosed in the washings is 0.063% by weight.
La conversion des chlorolactames est alors de 85% et le bilan chlore est de 100%.The chlorolactam conversion is then 85% and the chlorine balance is 100%.
Exemple comparatif 4c. On prépare une solution de cyclohexane à 10% en poids de lauryllactame contenant 0,103% en poids de chlore. Cette solution est ensuite alimentée en continu (82 g/h) dans le réacteur avec de l'hydrogène (0,5 1/h) sous 20 bar et 1800C dans un réacteur contenant 80 ml de catalyseur d'hydrogénation commercial Ni-NiO-SiO2-Al2O3.Comparative Example 4c. A solution of cyclohexane containing 10% by weight of lauryl lactam containing 0.103% by weight of chlorine is prepared. This solution is then fed continuously (82 g / h) into the reactor with hydrogen (0.5 l / h) at 20 bar and 180 0 C in a reactor containing 80 ml of commercial hydrogenation catalyst Ni NiO-SiO 2 -Al 2 O 3 .
Le mélange issu du réacteur est prélevé à différents temps de réaction. Le mélange est d'abord décanté pour séparer les phases liquide et gazeuse. Le lauryllactame est ensuite récupéré après évaporation du solvant. Les cristaux obtenus sont lavés avec de l'eau pour éliminer les sels produits.The mixture from the reactor is taken at different reaction times. The mixture is first decanted to separate the liquid and gaseous phases. Lauryllactam is then recovered after evaporation of the solvent. The crystals obtained are washed with water to remove the salts produced.
On évalue ici la performance de la réaction en fonction du temps de contact des réactifs .The performance of the reaction is evaluated here as a function of the contact time of the reactants.
La quantité de chlorures récupérée à la sortie du réacteur ne constitue qu'une partie (<10%) du chlore initialement présent dans le lactame sous forme de chlore organique. Les chlorures formés s'accumulent sur le catalyseur conduisant à une dégradation de ses performances . Exemple 4 .The amount of chlorides recovered at the outlet of the reactor is only a part (<10%) of the chlorine initially present in the lactam in the form of organic chlorine. Chlorides formed accumulate on the catalyst leading to a degradation of its performance. Example 4
Dans les conditions de réaction décrites ci-dessus, on alimente une solution de cyclohexane contenant 1.2% en poids de tert-octylamine ( 0,930% en moles) et 10% de lauryllactame. La quantité initiale de chlore organique dans le lactame est de 0,1% en poids (soit 0,028% en moles dans la solution) . Au bout de 20 heures de fonctionnement, la teneur en chlore organique résiduel après purification est de 0,003% en poids. La quantité de chlorure dosée dans les eaux de lavage est 0,095% en poids. La conversion des chlorolactames est alors de 97% et le bilan chlore est de 98%. Après 250 heures de fonctionnement, la conversion est de 96% avec un bilan chlore de 97%.Under the reaction conditions described above, a solution of cyclohexane containing 1.2% by weight of tert-octylamine (0.930 mol%) and 10% of lauryllactam is fed. The initial amount of organic chlorine in the lactam is 0.1% by weight (ie 0.028 mol% in the solution). After 20 hours of operation, the residual organic chlorine content after purification is 0.003% by weight. The amount of chloride dosed in the washings is 0.095% by weight. The chlorolactam conversion is then 97% and the chlorine balance is 98%. After 250 hours of operation, the conversion is 96% with a chlorine balance of 97%.
Exemple 5 : avec liquide ionique et sans aminé Dans un autoclave en acier inoxydable on charge sous atmosphère d'argon pour être à l'abri de l'humidité :Example 5: with ionic liquid and without amine In a stainless steel autoclave is charged under an argon atmosphere to be protected from moisture:
50 g de bmimPFβ , 2.64 g de catalyseur Pd / C et 5 g de lactame chloré (0.17 % de chlore total) .50 g of bmimPFβ, 2.64 g of Pd / C catalyst and 5 g of chlorinated lactam (0.17% total chlorine).
On pressurise l'autoclave avec 20 bar d'hydrogène et on chauffe le milieu réactionnel à 1000C pendant 6 heures sous agitation et sous 20 bar d'hydrogène.The autoclave is pressurized with 20 bar of hydrogen and the reaction medium is heated at 100 ° C. for 6 hours with stirring and under 20 bar of hydrogen.
Apres réaction on ajoute 50g de méthanol pour fluidifier le milieu et on filtre pour isoler le catalyseur.After reaction, 50 g of methanol are added to thin the medium and filtered to isolate the catalyst.
Le méthanol est évaporé sous vide et lactame cristallisé est filtré et lavé avec un peu d'acétonitrile et avec de l'eau puis séché à l'étuve à 800C .The methanol is evaporated under vacuum and crystallized lactam is filtered and washed with a little acetonitrile and with water and then dried in an oven at 80 0 C.
Sa teneur en chlore total est de 0.005 % au lieu de 0.17 % avant traitement soit un taux de conversion du chlorolactame en lactame de 97%..' Exemple 5c : comparatifIts total chlorine content is 0.005% instead of 0.17% before treatment, ie a conversion rate of chlorolactam to lactam of 97%. Example 5c: Comparative
On procède exactement comme pour l'exemple 5 mais en remplaçant le liquide ionique par 50 g de cyclohexane.The procedure is exactly as in Example 5 but replacing the ionic liquid with 50 g of cyclohexane.
La teneur en chlore total du lactame après traitement et lavage à l'eau est de 0.13 % au lieu de 0.17% avant traitement soit un taux de conversion du chlorolactame en lactame de 23.5%. The total chlorine content of the lactam after treatment and washing with water is 0.13% instead of 0.17% before treatment a conversion rate of chlorolactam to lactam of 23.5%.

Claims

REVENDICATIONS. CLAIMS.
1. Procédé de purification de lactames cycliques contenant 6 à 12 atomes de carbone et contenant des chlorolactames comme impuretés, par réaction d'hydrogénation en présence d'un catalyseur métallique, d'un solvant et d'un composé ayant un reste -NH2,-NH- ou -N< dans lequel,1. Process for purifying cyclic lactams containing 6 to 12 carbon atoms and containing chlorolactams as impurities, by hydrogenation reaction in the presence of a metal catalyst, a solvent and a compound having a residue -NH 2 , -NH- or -N <wherein
-le reste -NH2, -NH- ou -N< est celui d'une aminé de capture de l'HCl généré pendant la réaction d'hydrogénation, etthe residue -NH 2 , -NH- or -N <is that of an amine for capturing the HCl generated during the hydrogenation reaction, and
-le solvant organique est un solvant capable de solubiliser le chlorhydrate d'aminé formé par la capture de l'HCl par l'aminé, etthe organic solvent is a solvent capable of solubilizing the amine hydrochloride formed by the capture of HCl by the amine, and
-le ratio molaire représenté par le % d'aminé exprimé en mole sur le % de chlore organique élémentaire sous forme de chlorolactame exprimé en mole, est supérieur ou égale à 0,5.the molar ratio represented by the% of amine expressed in moles relative to the% of elemental organic chlorine in the form of chlorolactam expressed in moles, is greater than or equal to 0.5.
2. Procédé selon la revendication 1 dans lequel le ratio molaire est compris entre 1 et 100 et de préférence compris entre 5 et 40.2. Method according to claim 1 wherein the molar ratio is between 1 and 100 and preferably between 5 and 40.
3. Procédé selon la revendication 1 ou 2 dans lequel l'aminé est choisie parmi le groupe des alkylamines primaires, secondaires et tertiaires linéaires ou ramifiées RiNH2 , R1R2NH , RxR2R3N avec R1=CnH2n+I n=2 à 12 , R2=CmH2ra+1 m=l à3. Method according to claim 1 or 2 wherein the amine is selected from the group of primary, secondary and tertiary linear or branched alkylamines RiNH 2 , R 1 R 2 NH, R x R 2 R 3 N with R 1 = C n H 2n + I n = 2 to 12, R 2 = C m H 2ra + 1 m = 1 to
3 , R3=CpH2P+1 p=l à 3 .3, R 3 = C p H 2 P +1 p = 1 to 3.
4. Procédé selon l'une des revendications 1 à 3 dans lequel l'aminé est la tert-octylaminé.4. Method according to one of claims 1 to 3 wherein the amine is tert-octylamine.
5. Procédé selon l'une des revendications 1 à 4 dans lequel le solvant organique est choisi parmi le groupe constitué par les solvants hydrocarbonés saturés aliphatiques acycliques ou cycliques, les solvants aromatiques, les liquides ioniques.5. Method according to one of claims 1 to 4 wherein the organic solvent is selected from the group consisting of saturated aliphatic hydrocarbon solvents acyclic or cyclic, aromatic solvents, ionic liquids.
6. Procédé selon la revendication 5 dans lequel le solvant organique est le cyclohexane.The process of claim 5 wherein the organic solvent is cyclohexane.
7. Procédé de purification de lactames cycliques contenant 6 à 12 atomes de carbone et contenant des chlorolactames comme impuretés, par réaction d'hydrogénation en présence d'un catalyseur métallique, d'un solvant et d'un composé ayant un reste -NH- dans lequel, le reste -NH- est celui du lactame présent ou formé pendant la réaction d'hydrogénation et le solvant organique est un liquide ionique capable de solubiliser le chlorhydrate de lactame formé.7. Process for purifying cyclic lactams containing 6 to 12 carbon atoms and containing chlorolactams as impurities, by hydrogenation reaction in the presence of a metal catalyst, a solvent and a compound having a residue -NH- wherein the -NH- residue is that of the lactam present or formed during the hydrogenation reaction and the organic solvent is an ionic liquid capable of solubilizing the lactam hydrochloride formed.
8. Procédé selon la revendication 5 ou 7 dans lequel le solvant organique est un liquide ionique choisi parmi le groupe constitué par les liquides ioniques comprenant un dérivé dialkylimidazolium de formule I ou II8. The method of claim 5 or 7 wherein the organic solvent is an ionic liquid selected from the group consisting of ionic liquids comprising a dialkylimidazolium derivative of formula I or II
ACI Θ ACI Θ
I II dans lesquellesI II in which
R est un groupe CH3 , - (CH2) n-CH3 , -CH2-CnF2n+I , phényl avec n étant un ent ier compris entre 1 et 10 , et A représente AlCl3 , SbCl3F2 , TaCl5 , TaF5 , NbCl5 , TiCl4 , B représente SbF5 , BF4 , PF6 , CF3SO3 . R is a CH 3 group, - (CH 2 ) n -CH 3 , -CH 2 -C n F 2n + I, phenyl with n being a star between 1 and 10, and A represents AlCl 3 , SbCl 3 F 2 , TaCl 5 , TaF 5 , NbCl 5 , TiCl 4 , B represents SbF 5 , BF 4 , PF 6 , CF 3 SO 3 .
9. Procédé selon la revendication 8 dans laquelle le liquide ionique est formé par l'association entre le cation dialkyl imidazolium de formule I avec R tel que défini dans la revendication 8 et un anion hexafluoroborate BF6 ou bien un anion hexafluorophosphate PF6-9. The method of claim 8 wherein the ionic liquid is formed by the combination of the dialkyl imidazolium cation of formula I with R as defined in claim 8 and an anion hexafluoroborate BF 6 or an anion hexafluorophosphate PF 6 -
10. Procédé selon l'une des revendications 1 à 8 dans lequel la température est comprise entre 100 et 2500C.10. Method according to one of claims 1 to 8 wherein the temperature is between 100 and 250 0 C.
11. Procédé selon l'une des revendications 1 à 10 dans lequel le lactame est le lauryl-lactame ou le caprolactame.11. Method according to one of claims 1 to 10 wherein the lactam is lauryl-lactam or caprolactam.
12. Procédé de purification selon l'une des revendications 1 à 11 dans lequel le lactame à purifier contient jusqu'à 5% en poids de chlorolactame.12. Purification process according to one of claims 1 to 11 wherein the lactam to be purified contains up to 5% by weight of chlorolactam.
13. Procédé de purification selon l'une des revendications 1 à 12 dans lequel l'étape d'hydrogénation s'effectue en faisant passer en continu un débit de lactame dans un solvant contenant éventuellement l'aminé avec de l'hydrogène sur un catalyseur. 13. Purification process according to one of claims 1 to 12 wherein the hydrogenation step is carried out by continuously passing a lactam flow in a solvent optionally containing the amine with hydrogen on a catalyst .
EP05788450A 2004-07-16 2005-07-12 Method for catalytic hydrogenation purification of lactam containing chorolactam impurities Not-in-force EP1773765B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0407918A FR2873117A1 (en) 2004-07-16 2004-07-16 PROCESS FOR THE CATALYTIC HYDROGENATION PURIFICATION OF LACTAM CONTAINING CHLOROLACTAM IMPURITIES
PCT/FR2005/001794 WO2006016060A2 (en) 2004-07-16 2005-07-12 Method for catalytic hydrogenation purification of lactam containing chorolactam impurities

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EP1773765B1 EP1773765B1 (en) 2008-04-23

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Cited By (2)

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EP3498759A1 (en) 2017-12-13 2019-06-19 Evonik Degussa GmbH Method for the preparation of polymers from monomers comprising laurolactam
EP3498758A1 (en) 2017-12-13 2019-06-19 Evonik Degussa GmbH Method for the preparation of polymers from monomers comprising laurolactam

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DE102007017872A1 (en) * 2007-04-13 2008-10-16 Linde Ag Process for the inertization of an oxygen-sensitive catalyst

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JPH0737633B2 (en) * 1986-06-12 1995-04-26 麒麟麦酒株式会社 Method for improving aroma of hop essential oil
JPH0623743B2 (en) * 1989-06-29 1994-03-30 株式会社島津製作所 Sample introduction device
DE3925575A1 (en) * 1989-08-02 1991-02-07 Basf Ag PROCESS FOR CONTINUOUS CLEANING OF CAPROLACTAM
JP2003313171A (en) * 2002-04-23 2003-11-06 Kuraray Co Ltd Method for producing n-alkyl-n'-alkylimidazolium salt

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3498759A1 (en) 2017-12-13 2019-06-19 Evonik Degussa GmbH Method for the preparation of polymers from monomers comprising laurolactam
EP3498758A1 (en) 2017-12-13 2019-06-19 Evonik Degussa GmbH Method for the preparation of polymers from monomers comprising laurolactam

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JP4865708B2 (en) 2012-02-01
WO2006016060A8 (en) 2007-02-01
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DE602005006286T2 (en) 2009-05-20
WO2006016060A3 (en) 2006-04-20
JP2008505165A (en) 2008-02-21
ATE393143T1 (en) 2008-05-15
FR2873117A1 (en) 2006-01-20
WO2006016060A2 (en) 2006-02-16
CN101018767A (en) 2007-08-15
KR20070033464A (en) 2007-03-26
EP1773765B1 (en) 2008-04-23

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